Lithium-ion mixed conductor membrane improves the performance of lithium-sulfur battery and other energy storage devices

Abstract

A lithium ion mixed conduction membrane includes an optional polymeric binder and a partially lithiated ion conductive material having lithium ion conductivity and electrical conductivity dispersed within the polymeric binder that is capable of improving the performance and cycle life of lithium-sulfur rechargeable batteries and other batteries exhibiting the polysulfide shuttle. One or more lithium ion conduction membranes are placed between the positive and negative electrodes, or adjacent to the negative electrode of a battery and in particular, of a lithium sulfur battery.

What is claimed is: 
     
       1. A lithium ion mixed conduction membrane comprising:
 a polymeric binder; and 
 a lithium ion conductive material having lithium ion conductivity and electrical conductivity dispersed within the polymeric binder, the lithium ion conductive material being partially lithiated in an amount from 35 mole percent to 90 mole percent per mole of lithium in the lithium ion conductive material when the lithium ion conductive material is fully lithiated wherein the lithium ion conductive material is selected from the group consisting of wherein the lithium ion conductive material is selected from the group consisting of Li z MnO 2 , Li 2z MnO 3 , Li z Co 2 O 4 , Li z FeSO 4 F, Li z VPO 4 F, Li z MoS 2  and combinations thereof, with z being from 0.3 to 0.9 and wherein the lithium ion conductive is partially lithiated such that the electrode potential of the lithium ion mixed conduction membrane does overlap with the electrode potential range of a sulfur-containing cathode when the lithium ion mixed conduction membrane is positioned in a battery including the sulfur-containing cathode. 
 
     
     
       2. The lithium ion mixed conduction membrane of  claim 1  having an electrode potential at least 3.3 volts higher than the electrode potential of a Li + /Li electrode. 
     
     
       3. The lithium ion mixed conduction membrane of  claim 1  wherein z is from 0.4 to 0.8. 
     
     
       4. The lithium ion mixed conduction membrane of  claim 1  wherein the polymeric binder is an electrically insulating polymer. 
     
     
       5. The lithium ion mixed conduction membrane of  claim 1  wherein the polymeric binder is polyvinylidene fluoride. 
     
     
       6. A battery comprising:
 a sulfur-containing positive electrode including a sulfur-carbon composite supported on an aluminum foil or grid; 
 a negative electrode; and 
 a mixed conduction membrane interposed between the sulfur-containing positive electrode and the negative electrode, the mixed conduction membrane including 
 a polymeric binder; and 
 a lithium ion conductive material having lithium ion conductivity and electrical conductivity dispersed within the polymeric binder, the lithium ion conductive material being partially lithiated in an amount from 35 mole percent to 90 mole percent per mole of lithium in the lithium ion conductive material when the lithium ion conductive material is fully lithiated and wherein the lithium ion conductive is partially lithiated such that the electrode potential of the mixed conduction membrane does overlap with the electrode potential range of the sulfur-containing positive electrode when the battery is operated, wherein the lithium ion conductive material is selected from the group consisting of Li z MnO 2 , Li 2z MnO 3 , Li z Co 2 O 4 , Li z FeSO 4 F, Li z VPO 4 F, Li z MoS 2  and combinations thereof, with z being from 0.3 to 0.9. 
 
     
     
       7. The battery of  claim 6  wherein the negative electrode includes lithium metal or lithium ions. 
     
     
       8. The battery of  claim 6  wherein the mixed conduction membrane has and electrode potential at least 3.3 volts higher than the electrode potential of the negative electrode. 
     
     
       9. The battery of  claim 6  wherein the polymeric binder is an electrically insulating polymer. 
     
     
       10. The battery of  claim 6  further comprising a first electrolyte layer interposed between the sulfur-containing positive electrode and the mixed conduction membrane. 
     
     
       11. The battery of  claim 10  further comprising a second electrolyte layer interposed between the negative electrode and the mixed conduction membrane. 
     
     
       12. The battery of  claim 11  wherein the first electrolyte layer and the second electrolyte layer each independently include a polymeric substrate with an electrolyte solution imbibed therein. 
     
     
       13. The battery of  claim 10  wherein the first electrolyte layer is a lithium ion-containing solution. 
     
     
       14. A battery comprising:
 a positive electrode; 
 a negative electrode; and 
 a first mixed conduction membrane interposed between the positive electrode and the negative electrode; 
 a second mixed conduction membrane interposed between the first mixed conduction membrane and the negative electrode, the second mixed conduction membrane including a partially or fully lithiated ion conductive material; 
 a first electrolyte layer interposed between the positive electrode and the first mixed conduction membrane; 
 a second electrolyte layer interposed between the first mixed conduction membrane and the first mixed conduction membrane, wherein the first mixed conduction membrane includes: 
 an polymeric binder; and 
 a lithium ion conductive material having lithium ion conductivity and electrical conductivity dispersed within the polymeric binder, the lithium ion conductive material being partially lithiated in an amount from 35 mole percent to 90 mole percent per mole of lithium in the lithium ion conductive material when the lithium ion conductive material is fully lithiated, wherein the lithium ion conductive is partially lithiated such that the electrode potential of the first mixed conduction membrane does overlap with the electrode potential range of a sulfur-containing cathode when the battery is operated, wherein the lithium ion conductive material is selected from the group consisting of Li z MnO 2 , Li 2z MnO 3 , Li z Co 2 O 4 , Li z FeSO 4 F, Li z VPO 4 F, Li z MoS 2  and combinations thereof, with z being from 0.3 to 0.9. 
 
     
     
       15. The battery of  claim 14  wherein the negative electrode includes lithium metal or lithium ions. 
     
     
       16. The battery of  claim 15  wherein the first mixed conduction membrane has and electrode potential at least 3.3 volts higher than the electrode potential of the negative electrode. 
     
     
       17. The battery of  claim 14  wherein the polymeric binder is an electrically insulating polymer. 
     
     
       18. The battery of  claim 14  wherein the first electrolyte layer and the second electrolyte layer are each independently a porous separator with electrolyte imbibed therein or an electronically insulating electrolyte layer. 
     
     
       19. The battery of  claim 18  wherein the electrolyte is a lithium ion-containing solution. 
     
     
       20. The battery of  claim 18  wherein the second mixed conduction membrane includes a partially lithiated ion conductive material. 
     
     
       21. The battery of  claim 18  wherein the second mixed conduction membrane includes a fully lithiated ion conductive material.